Refining waxes



REFINING WAXES Filed April4 6, 1946 PARAFFIN Dls-rnLLA-l-E.

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NEuTRALlzING QEluNNm Ovav. E aamassl CAusfrm BAUM-ra DmzcoLA-HQN QEF'INED HEAT-.AND I HT-STAELE WAXy RobeKrt d TI'ZcJcKea Herman J'. 'ZoeZZer big Clbborng 511V ent/ors by ltering the chilled mixture.

Patented Oct. 28, 1947 REFINING WAXES Robert A. Macke, Westfield, and Herman J. Zoeller, Union, N. J., assignors to StandardOil Development Company, a corporation of Dela- Ware Application April 6, 1946, Serial No. 660,040

11 claims.

The present invention is concerned with the refining of paraiin waxes which are segregated from petroleum or other mineral oil sources. The invention more particularly relates to an improved process comprising a particular arrangement and sequence of stages by lwhich waxes having a high heat and light stability are secured.

It is well known in the art to separate waxy constituents from petroleum oils by various processes and to rene the crude waxes separated by subjecting them to carefully regulated heat treatment, usually in a sweater house. Separation of the waxy constituents from -feed oils by conventional methods usually comprises chilling the waxy feed oil to temperatures at whichvthe wax crystallizes and passes out of solution, followed The waxes so obtained usually retain appreciable amounts of the oily constituents, the concentration of which may vary from about to about 50%, or more, based upon the oily wax. These waxes, termed slack waxes, due to the amount of oil present, are semi-solid and unctuous in nature, particularly so when the amount of oil present is relatively high. The slack wax cake is removed from the filter press, melted in a suitable receptacle and conveyed in a molten state to sweating apparatus, the conventional form of which comprises a multiplicity of shallow metal pans stacked one above the other. Each pan is equipped with a false perforated bottom and a continuous coil of pipe through which a heating or cooling fluid may be circulated. The stack of pans is closed within the building, commonly known as a sweater house. The usual practice in charging the sweater pans is to ll each pan with water to the height of the false bottom which is withdrawn from the bottom of the pan after the wax charge has solidified. The molten wax is then charged to the pan in such a way that it floats upon the water and that the interface between the wax and oil is slightly above the perforated plate. Under these conditions the pipe coil which is disposed immediately above the false bottom is submerged in the wax.

The molten wax is solidied =by circulating cooling water, or an equivalent cooling medium through the coil and by means of cool air which is passed through the sweater house. After the crude wax is solidified, it is sweated and the oily constituents removed by gradually increasing the vsequent sweating of the crude scale wax or by temperature of the oil-wax cake by circulating a of the crude Wax cake rises, the oily constituents are rst removed. After removal of an appreciable amount of the oily constituents, waxes of gradually increasing melting points are removed. These waxes contain gradually diminishing percentages of oil as the sweater house temperature and the melting points of the fused waxes increase. Finally, the sweating operation progresses to the point where only the porous structure of the highest melting point wax remains in the solid stage on the perforated false bottom since the other wax fractions have melted out and have been drained off by grades to storage receptacles. The remaining solid, relatively high melting point wax is substantially oil-free and is known in the art as crude scale wax. Crude scale wax contains approximately 2% of oil based upon the wax'and is hard and rlrm, and generally possesses some discoloration. This crude scale wax is subjected to further sweating in order to remove the remainder of the oil, and to produce a refined high grade wax.

The oil can also be largely removed from oily wax, either crude scale Wax or slack wax, by the so-called solvent de-oiling process, in which relined waxes are produced by solvent recrystallization from solvents such as ketones, benzolketone mixtures, chlorinated solvents, hydrocarbons, etc.

However, the rened waxes secured by a subsolvent de-oiling are not entirely satisfactory with respect to their stability when subjected to heat and light. The instability of these waxes is a particular disadvantage since it renders them unt for many uses, such as the coating of paper for use in conjunction with the handling of food materials. The instability of petroleum waxes with respect to heat and light is aggravated when the waxes are secured from particular crudes such as a Panhandle crude, a Salt Flat crude, or a Reagan type crude.

In order to overcome these inherent disadvantages and to improve the quality of the nal wax produced, various proposals have been made. For example, in the conventional procedure slack wax is acid treated, neutralized, and water washed, followed by sweating to crude scale, which in turn is sweated to refined wax. An alternate processing scheme involves acid treating the crude scale, caustic neutralizing, and water washing, followed by sweating to refined wax. However, these operations do not produce a final wax product which has a satisfactory heat and light stability when the wax is derived from said specific crude sources. Similar procedures using solvent de-oiling instead of sweating likewise do not give satisfactory results.

We have, however, now discovered that providing a particular sequence and arrangement of stages be employed it is possible to produce a final wax product of especially hi'gh quality which is particularly stable 'with respect "to light "and heat. purposes for which waxes produced by the conventional procedure would not be at all satisfactory. For example, the waxesproduced by our process are particularly desirable -for'utilfzation in conjunction with the preservation of food stocks, medicinals, and the like. In accordance with our process a petroleum wax in the processing of the same is distilled over caustic. IAlrthough the slack wax may be distilled over caustic providing a critical amount of caustic be employed, a preferred'modication of our process, asdisclosed and claimed in application 'Sei'. No. 403,818, filed July 2fi,y1941, whichh'aslnovv becoinevPatent No. 2,397,969, dated April 9,. 194'6, ,of which the present application is a continuation-in-part, comprises acid ltreating 'crude scale wax, removing the acid, lrerunning "the acid treated prpduet over excess caustic, followed by sweating the overhead product 'under conventional conditions to produce 'a refined wax prod- 'uct of especially high quality. y

Another preferred modification, 'which is the subject of the present application, lcomprises the lcombination process of solvent de-oiling 'an oily wax and rerunning lt over excess caustic. The

'preferred complete process as illustrativly outoiling being .preferably carried out in one or more stages until the oil content of the Wax-isreduced 'at least down to 5 or 10%, and preferably down to 2% or less, as for exampler 0.5%, then acid Our wax is, therefore, very desirable for u solvent, per volume of wax, preferably at about y as treating the resultant de-oiled wax, to remove aromatic and unsaturated hydrocarbons and other constituents, if any, which are reactive with strong Asulfuric acid, and which were not previously removed by the solvent de-oili'ng step, then after removing acid sludge, neutralizing the acid- ,y

be carried out in a single stage, but preferably lis carried out in several stages, 4or else-by continuous countercurrent extraction. The method of operating in several stages preferably comprises heating the oily wax, i. e. slack wax, which may contain 5 to 50%, e. g. about 10%, of oil, with 5to 1'5 volumes, preferably about 10 volumes, of a suitable solvent such as secondary butyl acetate .per volume of Wax, up to a solution temperature such as in the general range of about -175 F., preferably about F., followed by cooling to one of the primary features of this invention, may

having about "1% of oil `in this partially de-oiled wax, and then v'repuddliilg the latter with an additionalamount of about 5 to 15 or more, e. g. about 10, volumes of the same or similar type of 10 to 30 F., e.` g. -about 20 F., or other suitable 'tem'peraturezbelow the wax-solution temperature, and nal-ly filter Vpressing ythe de-oiled wax to remove the 'solvent and the oil dissolved therein, thus producing a de-oiled wax containing genierally substantially less than 1%, e. g. about 0.5%fof oil.

The solvent to be used in the above described solvent de-oiling process, may -nOt only be seconda'ry butyl 'acetate but other esters having about 4 to 10,' preferably about 5 to 8 carbon atoms, such as isopropyl acetate, amyl acetate, isopropyl propionate, isopropyl butyrate, hexyl acetate, etc., as well as other types of organic solvents 'such as acetone, lmethyl ethyl ketone, bnZol-ketone mixtures, chlorinated solvents, or hydrocarbon liquids or normally gaseous lique- 'able hydrocarbon gases such as propane, or

' respective steps may comprise any suitable numb'er and arrangement of stages. The invention essentially comprises solvent cle-oiling the wax and distilling it over caustic, preferably, an alkali metal hydroxide, e. g. sodium or potassium hydroxide, solution, or suspension. Alkali metal c'arbonates as, for example, sodium carbonate may also-be employed.

Although the operation may be adapted for the treatment of waxes segregated fromY any mineral oil, it is particularly suitable for the treatment of waxes separated from .petroleum oils, especially of the Panhandle type, which waxes are quite unstable with respect to heat and light. Although the Panhandle and other certain crudes have been mentioned above as being particularly Ysuited for the purposes of this invention, the process is considered broadly applicable for re- -fining a distillable petroleum Iwax which normally has poor heatand light-stability even vafter acid treatment, de-oiling, and bauxite ltering. The slack waxes segregated from petroleum oils by conventional operations usually contain from about 5% to 50% of oil. These waxes when 'swe'ated yield from aboutV 25% to 75% crude vscale wax, based upon the slack wax. The crude scale waxes when sweated result in a yield of about 20% to 65% of rened waxes based upon theslack wax.

Although it has been suggested above that the solvent de-oiling step be used as the essential method of removing oil from the oily slack wax,

and that this Vsolvent de-oiling step should precede the acidtreatment and rerunning over excess caustic, this order of procedure is not absolutely essential, and other modified procedures may be used. For instance, if the slack wax to be used contains a relatively small amount of oil such as 5 to 10% or less, it may suitably be rened by acid treating, neutralizing, rerunning over excess caustic, and then solvent de-oiling, preferably followed by bauxite percolation. Also one may use a combination of sweating and solvent cle-oiling, such as by, first subjecting the oily'slack wax to a solvent de-oiling to reduce the oil content of the wax down to 1% or so, then acid treating, neutralizing, rerunning over excess caustic and then sweating to reduce the oil content down to the range of 0.1 to 0.2% or so, and finally bauxite percolating. If preferred, the sweating may be applied immediately after the solvent de-oiling, so that for instance a slack wax containing about of oil would be solvent de-oiled down to a 1% oil content, then sweated down to an 0.1 or 0.2% oil content and,-

then subjected to the acid treating, neutralizing, rerunning over excess caustic, and bauxite percolation. On the other hand, if preferred, the slack wax may first be sweated to a crude scale wax containing about 1 to 3% of oil, then acid treated, neutralized, rerun over excess caustic, and then solvent de-oiled, and finally subjected to bauxite percolation. A still further ymodification comprises subjecting the slack wax to an initial sweating to a crude scale wax andA then immediately solvent. de-oiling, and `then following with the other steps previously described, namely acid treating, neutralizing, re-

running over excess caustic and final bauxite percolation.

Although solvent de-oiling and sweating both accomplish a similar primary objective, namely reduction of the oil contentof an oily wax, there is reason to believe that they function in a slightly different way, and that the small amount of residual oily constituents left after subjecting a wax to one of these steps, is not exactly the same as after subjecting it to the other. In any event,

the solvent de-oiling, with or without sweating,

and together with acid treating, still leaves some1 constituents in the wax which tend to impair its heat and light stability, so that rerunning over excess caustic must be used to remove this other type of impurities.

The acid employed in the acid treating stage may comprise any suitable mineral acid but it is preferred to employ a sulfuric acid having a concentration in the range from about 83% to about 104%. The amount of acid employed may be in the range from about 3 pounds to about 50 pounds, preferably about 5 to 40 pounds, of acid per hundred gallons of wax. In general, it is preferred to contact the wax and the acid at a temperature in the range from about 150 F. to about 200 F.

The alkali solution employed in the distillation stage and in the neutralization stage may comprise any suitable alkali. In the distillation stage, an excess amount of the alkali is employed whereas in the neutralization stage an amount is used which is necessary to neutralize the acidic constituents. Although potassium hydroxide or sodium carbonate solutions may be employed, we prefer to use sodiumhydroxide solutions such as those having a concentration in the range from` about 34 to about 38 Baume. When utilizing excess sodium hydroxide it is preferred to use from 0.01 to 0.5% excess. For example, when directly distilling the slack wax over caustic the amount of excess caustic employed should be in the range from about 0.2 to 0.3%. Also about 0.01 to 0.1% excess caustic should be employed with the acid treated crude scale wax or solvent de-oiled wax. The distillation operations over the caustic are conducted under either at- '6 mospheric or vacuum conditions and at a coil outlet temperature in the range from about 600 F..t0 about 800 F.

In order to illustrate the invention further, the following examples are given.

Example 1 A parailin distillate, i. e. a wax-containing lubricating oil fraction, obtained from a Panhandle crude petroleum oil, and containing about 20% of wax, was solvent dewaxed by heating with two volumes of secondary butyl acetate per volume of parafn distillate, to a temperature of about F. to insure complete solubility, and then cooling to about 20 F. to precipitate paraffin wax which was then filtered out in the form of a slack wax containing about 10% of oil. This was then solvent de-oiled by heating with 10 volumes of the same so1vent,i. e. secondary butyl acetate, per volume of slack wax, to about 150 F. to insure complete solution of the Wax in the solvent, and then the solution was cooled to a crystallization temperature of about 20 F. and filter pressed. The resultant partially de-oiled wax cake, ycon-- taining about 1% of oil, was then repuddled with an additional amount of the same solvent, using 10 volumes of solvent per volume of wax, at the same temperature of 20 F. and the mixture was then filter pressed without the use of any wash solvent, resulting ina final de-oiled wax containing about 0.5% of oil.

This de-oiled wax was then treated with 30 pounds of 98% sulfuric acid per 100 gallons of wax at a temperature of about 16S-170 F., the sludge settled and removed and the acid-treated wax was neutralized with dilute aqueous caustic sodaV of about 5 degree Baum' concentration, and divided into two batches, one of which was directly vbauxite filtered to a yield of 25 tons of refined wax per ton of bauxite, and the other batch was rerun over 0.2 weight per cent excess caustic soda, in the form of a substantially saturated aqueous caustic solution to give an overhead distillate fraction of 5 to 90% which was then bauxite filtered to the same yield of 25 tons per ton.

These two refined waxes, the one Without and the other with rerunning over excess caustic, were then subjected to inspection and stability test with the following results:

Without rerunning Melting Point, F Per cent Oil-ASTM D721-44 0 Color-Saybolt Heat Stability: 1

Color Copper Strip Tarnlshed.

Llght Stabllity: 2 Color 17% T. R.. 0 S.

sponding to an absolute color greatly in excess of 700, after the heat stability test and also unsatisfactory light stability because it developed a T. R. color of 17% which corresponds to an absolute color of about 30 or 31 after the light stability test; whereas the refined wax which had been given a similar treatment except with the additional rerunning over excess caustic, showed amaca? scale, all three of these scales are tabulated here- Awith in position to show their correlation with leach other:

Absolute Color Scale ."3 6 l. l 2. 3 3. 3 4. 2 5. 3 6.9 8.3 8.8 22 13. 2 20 27.0 18 41. o 16 54. 14 81.0 12 162.0 l0' 350. o 8. 465. 0 6 700.0 4

Example 2 In applying the invention Ato the use o'f `p'r'opane in the solvent deeoiling step, itis preferable to use as the waxy oil starting material a waxcontaining lubricating oil. This is preferably dewaxed by a solvent dewaxing using the same solvent, i. e. propane, for instance using a dilution of 3 volumes of liqueedpropane to 1 volume of waxy oil, heated to a solution ten'ope'raturev` of,

yabout 120 F. under a pressure of about 250 lbs/sq. in., then cooled to a temperature within the 4range of 0 F. to 50 F., and filtered. The resulting wax cake which may contain Vabout of oil, is then heated to about 130 F. and dissolved in 5 volumes of liquefied propane per volunie of wax, at that temperature, under a pressure of about 280 lbs/sq. in. The solution is then cooled to about 0 F. to precipitate ythe wax, and ltered, the wax being Washed with about -2 yolurnes of propane at the same temperature, AThe resulting partially de-oiled wax, now containing about 1% of oil, may then be repuddled at 0 F. in approximately 5 volumes of liquefied propane solvent. This mixture is then filtered, and washed with about 2 volumes of propane, thereby .producing a de-oiled wax containing less than about 0.5% oil. This cle-oiled wax is then treated with acid, neutralized, and rerun over "excess caustic as in Example 1.

Example 3 A ben'zol-ketone solvent, for instance one consisting of a mixture of about 60% by volume of methyl ethyl ketone with 40% by volume of ben- Zol, may be used with substantially identical procedure as in Example 2 except that atmospheric pressure can be used, and that the wax precipitation and filtration can be carried out at about 20 F. instead of 0 F. or lower. Vacuum filtration may be used if desired. The deeoiled Wax is then -furthei` refined by the acid-treating, neutalizing and rerunning over excess caustic in the -sam'e way as in Examplel.

-It isnot intended that this invention be limited to Fthe specific materials which have been mentioned -merely-for the sake of illustration but only by the Aappended claims in which it is intended to claim all novelty inherent in the invention as well as all modifications coming within the scope 'and spirit of the invention. Y

Wha't :We claim is: v

1. Process for refining a distillatable petroleum wax which normally has poor heat and llight stability event after acid treatment, de-oiling `and bauxite filtering, which comprisessubjecting ^said wax to a combination of two operations, one

of which comprises solvent de-oiling, and -the other of which consists in distilling said wax over an alkali. using a sufficient excess of valkali to impart the desired heat stability and light stability to said wax, and removing Aand "condensing the distilled wax vapors.

2. VProcess for the lproduction'of highly refined waxes which comprises segregating oily wax from oils containing 'the same, de-oiling said waxby an operation comprising at least a solvent deoiling step, to produce an at least partially deoiled wax containing not more oil than nor- Vmally present in a `crude scale wax, then acid treating said de-oiled wax, neutralizing it, and distilling it over exces's'alkali, and recovering the overhead.

3. Process according to lclaim 2 in which the vvv'a'x'is distilled over about 0.1% excess sodium lhydroxide.

'4. Process vaccording to claim 2 followed by bauxite percolation.

5. Process according to claim -2 followed by sweating to a final oil content riot more than 6. Process vfortl'ie production of highly reiined paraffin wax from slack wax which comprises in sequence, solvent de-oiling, acid treating, neutralizing, distilling over excess alkali, and bauxite percolation.

7. Process 'according't'o -claim 6 using as solvent an ester having about 4 to 10 carbon atoms.

8. Process according to claim 6 using propane as solventfor the solvent de-oiling step.

9. Process for the production of a highly refined wax having satisfactory heat and light stability from a petroleum wax which normally has poor heat and light stability even after acid treatment, de-oiling, and bauxite filtering, which comprises solvent de-oiling said slack wax with about 2 to 10 volumes of secondary butyl acetate per volume of wax, by heating the wax and solvent to a solution temperature of about 150 F., cooling to a crystallization temperature of about 20 F. and filter pressing to obtain a partially de-oiled Wax cake, repuddling the latter with an additional amount of the same solvent, using about 2 to 10 volumes of solvent per volume of wax, at a temperature below the solution ternperature, and ltering to obtain a finallylde-oiled wax, subjecting the latter to acid treating using about 5 to 40 pounds of sulfuric acid having a concentration of about to 105%, per hundred gallons of wax at a temperature of about 13G-200 F., removing the resultant acid sludge and neutralizing the acid treated wax with aqueous caustic soda, and distilling the acid treated and neutralized wax over about 0.05 to 0.2% excess sodium hydroxide, to an overhead distillate fraction of about 5 to 90%, removing and condensing 9 the distilled wax vapors, and subjecting the condensed wax to bauxite percolation.

10. The process of preparing puried petroleum wax from waxy distillate obtained from a crude petroleum oil, which comprisesV subjecting said parafn distillate to dewaxing to produce a major proportion of oil and a minor proportion of an oily slack wax, subjecting the latter to solvent de-oiling, acid treating, neutralizing, distilling over excess alkali, and bauxite percolation, to produce a rened wax having satisfactory heat and light stability.

11. Process according to claim 2 in which the de-oiling operation also comprises a sweating step.

ROBERT A. MACKE. HERMAN J. ZOELLER.

REFERENCES CITED The following references are of record in the ille of this patent:

-UNITED STATES PATENTS Certicate of Correction Patent No. 2,429,727. October 28, 1947.

ROBERT A. MAOKE ET AL.

lt is hereby eertied that error appears in the printed specication of the above numbered patent requiring correction as follows: Column 8, line 14, claim 1, for the Word event read even; and that the saidvLetters Patent should be read With this grection therein that the same may conform to the record of the case in the Patent VSigned and sealed this 6th day of April, A. D. 1948.

[SEAL] THOMAS F. MURPHY,

Assistant Gommtssz'oner of Patents. 

